Abstract
Reaction of Ru(PPh 3) 3X 2 (X = Cl, Br) with equimolar picolinic acid (Hpic) in dichloromethane solution at ambient temperature gave diamagnetic [Ru(PPh 3) 2(pic)(H 2O)X], which in solution showed intense absorption bands in the visible region assigned to MLCT transitions. Each complex displayed a reversible ruthenium(II)-ruthenium(III) oxidation near 0.60 V vs SCE. Reaction of [Ru(PPh 3) 2(pic)(H 2O)X] with base eliminated a molecule of HX and then dimerized to produce the hydroxo-bridged [{Ru(PPh 3) 2(pic)(OH)} 2] complex. In solution it showed intense MLCT transitions in the visible region. Two successive quasi-reversible ruthenium(II)-ruthenium(III) oxidations were observed in this dimer at 0.75 V and 1.01 V vs SCE. Reaction of Ru(PPh 3) 3X 2 with two equivalents of Hpic in refluxing ethanol afforded [Ru(PPh 3) 2(pic) 2]. This diamagnetic complex exhibited several intense MLCT transitions in solution. The ruthenium(II)-ruthenium(III) oxidation took place reversibly at 0.54 V vs SCE in this complex.
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